Fluid catalytic cracking of oxygenated compounds

ABSTRACT

A process is disclosed for fluid catalytic cracking of oxygenated hydrocarbon compounds such as glycerol and bio-oil. 
     In the process the oxygenated hydrocarbon compounds are contacted with a fluid cracking catalyst material for a period of less than 3 seconds. 
     In a preferred process a crude-oil derived material, such as VGO, is also contacted with the catalyst.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation of application Ser. No. 12/377,388, now U.S. Pat.No. 8,207,385, filed Feb. 13, 2009, which is based on PCT InternationalApplication PCT/EP2007/058467, filed Aug. 15, 2007 which claims priorityfrom European Patent Application No. 06118982.5 filed on Aug. 16, 2006,the entirety of each of the foregoing applications is herebyincorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a process for production of olefins, aromatic,syn-gas (hydrogen, carbon monoxide), process heat, and coke byco-feeding oxygenated compounds, such as glycerol, carbohydrates, sugaralcohols or other oxygenated biomass-derived molecules such as starches,cellulose, and hemicellulose-derived compounds) with petroleum derivedfeedstocks in a modified fluid catalytic cracking process.

2. Description of the Related Art

Fluid catalytic cracking (FCC) is the most widely used process for theconversion of crude oil into gasoline, olefins and other hydrocarbons.The FCC process consists of two vessels coupled together as shown inFIG. 1. In the first reactor a hot particulate catalyst is contactedwith hydrocarbon feedstocks, thereby producing cracked products andspent coked catalyst. After the cracking reaction takes place thecatalyst is largely deactivated by coke.

The coked catalyst is separated from the cracked products, stripped ofresidual oil by steam stripping and then regenerated by burning the cokefrom the deactivated catalyst in a regenerator. The hot catalyst is thenrecycled to the riser reactor for additional cracking. A variety ofprocess configurations and catalysts have been developed for the FCCprocess. The heart of the FCC catalyst is a faujasite zeolite. Newmedium, large and extra-large pore zeolites are actively searched toachieve a higher flexibility in product distribution.

The European Commission has set a goal that by 2010, 5.75% oftransportation fuels in the EU will be biofuels. Blending biofuels withpetroleum based fuels will help to reduce dependence on imported crudeoil, reduce emission of greenhouse gases, and improve agriculturaleconomies. Using FCC processes for biomass conversion does not require asignificant capital investment, as FCC plants are already installed inpetroleum refineries. It would therefore represent a considerableadvance in the state of the art if efficient methods were developed touse the FCC process to convert biomass-derived molecules intotransportation fuels.

Several methods have been reported for conversion of biomass-derivedmolecules into liquid fuels using zeolite catalysts. Chen and Koenig inU.S. Pat. No. 4,933,283 and U.S. Pat. No. 4,549,031 (Mobil) report aprocess for conversion of biomass derived carbohydrates, starches andfurfural into liquid hydrocarbon products, CO, and coke, by passingaqueous streams over zeolite catalysts at 500° C.[Chen, 1986 #9; Chen,1990 #10] They observed that 40-66% of the carbon leaves the reactor ascoke when xylose, glucose, starch and sucrose are fed over a ZSM-5catalyst at 500° C.[Chen, 1986 #9] Other products formed includehydrocarbons, CO, and CO₂. Mixing the aqueous-carbohydrate streams withmethanol leads to lower levels of coke and higher levels of hydrocarbonsbeing formed.

Chen et al. report the major challenge with biomass conversion to be theremoval of oxygen from the biomass and enriching the hydrogen content ofthe hydrocarbon product. They define the effective hydrogen to carbonratio (H/C_(eff)) defined in Equation 1. The H/C_(eff) ratio of biomassderived-oxygenated hydrocarbon compounds is lower than petroleum-derivedfeedstocks due to the high oxygen content of biomass-derived molecules.The H/C_(eff) ratio of carbohydrates, sorbitol and glycerol (allbiomass-derived compounds) are 0, 1/3 and 2/3 respectively. TheH/C_(eff) ratio of petroleum-derived feeds ranges from 2 (for liquidalkanes) to 1 (for benzene). In this respect, biomass can be viewed as ahydrogen deficient molecule when compared to petroleum-based feedstocks.

$\begin{matrix}{{H/C_{eff}} = \frac{H - {2O} - {3N} - {2S}}{C}} & (1)\end{matrix}$where H, C, O, N and S are the moles of hydrogen, carbon, oxygen,nitrogen and sulfur respectively.

Glycerol is currently a valuable by-product of biodiesel production,which involves the transesterification of triglycerides to thecorresponding methyl or ethyl esters. As biodiesel production increases,the price of glycerol is projected to drop significantly. In fact, theprice of glycerol has already dropped by almost half over the last fewyears. [McCoy, 2005 #6] Therefore it is desirable to develop inexpensiveprocesses for the conversion of glycerol into chemicals and fuels.

Methods for conversion of solid biomass into liquids by acid hydrolysis,pyrolysis, and liquefaction are well known [Klass, 1998 #12]. Solidmaterials including lignin, humic acid, and coke are byproducts of theabove reaction. A wide range of products are produced from the abovereactions including: cellulose, hemicellulose, lignin, polysaccharides,monosaccharides (e.g. glucose, xylose, galatose), furfural,polysaccharides, and lignin derived alcohols (coumaryl, coniferyl andsinapyl alcohols).

Bio-oils, produced by fast pyrolysis or liquefaction of biomass, are amixture of more than 300 compounds. Bio-oils are thermally unstable, andneed to be upgraded if they are to be used as fuels. Bio-oils, andbio-oil components, can be converted to more stable fuels using zeolitecatalysts. [Bridgwater, 1994 #14] Reaction conditions used for the aboveprocess are temperatures from 350-500° C., atmospheric pressure, and gashourly space velocities of around 2. The products from this reactioninclude hydrocarbons (aromatic, aliphatic), water-soluble organics,water, oil-soluble organics, gases (CO₂, CO, light alkanes), and coke.During this process a number of reactions occur including dehydration,cracking, polymerization, deoxygenation, and aromatization. However poorhydrocarbon yields and high yields of coke generally occur under thesereaction conditions, limiting the usefulness of zeolite upgrading.

Bakhshi and co-workers studied zeolite upgrading of wood derivedfast-pyrolysis bio-oils and observed that between 30-40 wt % of thebio-oil formed coke or char. (Sharma and Bakhshi 1993; Katikaneni,Adjaye et al. 1995; Adjaye, Katikaneni et al. 1996) The ZSM-5 catalystproduced the highest amount (34 wt % of feed) of liquid organic productsof any catalyst tested. The products in the organic carbon were mostlyaromatics for ZSM-5, and aliphatics for SiO₂—Al₂O₃. Gaseous productsinclude CO₂, CO, light alkanes, and light olefins. Bio-oils arethermally unstable and thermal cracking reactions occur during zeoliteupgrading. Bakhshi and co-workers also developed a two-reactor process,where only thermal reactions occur in the first empty reactor, andcatalytic reactions occur in the second reactor that contains thecatalyst. (Srinivas, Dalai et al. 2000) The reported advantage of thetwo-reactor system is that it improved catalyst life by reducing theamount of coke deposited on the catalyst.

The transformation of model bio-oil compounds, including alcohols,phenols, aldehydes, ketones, acids, and mixtures, have been studied overHZSM-5 catalysts. (Gayubo, Aguayo et al. 2004; Gayubo, Aguayo et al.2004; Gayubo, Aguayo et al. 2005) Alcohols were converted into olefinsat temperatures around 200° C., then to higher olefins at 250° C.,followed by paraffins and a small proportion of aromatics at 350° C.(Gayubo, Aguayo et al. 2004) Phenol has a low reactivity on HZSM-5 andonly produces small amounts of propylene and butanes. 2-Methoxyphenolalso has a low reactivity to hydrocarbons and thermally decomposes,generating coke. Acetaldehyde had a low reactivity on ZSM-5 catalysts,and it also underwent thermal decomposition leading to coking problems.(Gayubo, Aguayo et al. 2004) Acetone, which is less reactive thanalcohols, converts into C₅₊ olefins at temperatures above 350° C. Theseolefins are then converted into C₅₊ paraffins, aromatics and lightalkenes. Acetic acid is first converted to acetone, and that then reactsas above. Products from zeolite upgrading of acetic acid and acetonegive considerably more coke than products from alcohol feedstocks. Thus,different molecules in the bio-oils have a significant difference inreactivity and coke formation rates.

Catalytic cracking of vegetable oil can be used to produce a liquid fuelthat contains linear and cyclic paraffins, olefins, aldehydes, ketones,and carboxylic acids. The cracking of vegetable oils has been studiedsince 1921, and pyrolysis products of vegetable oils were used as a fuelduring the 1^(st) and 2^(nd) World Wars. Both homogeneous andheterogeneous reactions are occurring during catalytic cracking ofvegetable oils. The pyrolysis reaction can be done with or without acatalyst, and a number of catalysts have been tested including HZSM-5,β-zeolite, and USY.^(60,61) Twaiq et al. used a ZSM-5 catalyst toproduce yields of 28, 9, and 5% gasoline, kerosene, and diesel fuelrespectively from a Palm oil feed. Lima et al. claim that pyrolysisproducts with a ZSM-5 catalyst and soybean and palm oil feedstock, havefuel properties similar to Brazilian Diesel Fuel.

SUMMARY OF THE INVENTION

This invention generally relates to a process for fluid catalyticcracking of oxygenated hydrocarbon compounds, comprising the step ofcontacting a reaction feed comprising an oxygenated hydrocarbon compoundwith a fluid cracking catalyst material for a period of less than 3seconds, at a temperature in the range of 300 to 700° C.

This invention more specifically relates to a process for production ofolefins, aromatic, syn-gas (hydrogen, carbon monoxide), process heat,alkanes, and coke by co-feeding of glycerol, carbohydrates, sugaralcohols or other biomass derived molecules with high concentrations ofoxygen (including starches, cellulose-derived compounds, andhemicellulose-derived compounds) with petroleum derived feedstocks in amodified fluid catalytic cracking process. Mixtures of these compounds,such as those found in bio-oils derived from pyrolysis or liquefaction,are also included in the biomass-derived oxygenate definition.

BRIEF DESCRIPTION OF THE DRAWINGS

A specific embodiment of the invention will be explained with referenceto the drawings, of which:

FIG. 1 is a flow diagram of a typical FCC process.

FIG. 2 is a flow diagram of a modified FCC process for co-feedingbiomass-derived oxygenated hydrocarbon compounds with petroleumfeedstocks.

FIG. 3 shows hydrogen producing reactions for catalytic cracking ofbiomass.

FIG. 4 shows hydrogen consuming reactions for catalytic cracking ofbiomass.

FIG. 5 shows the effect of catalyst composition on the catalyticcracking of a 50 wt % glycerol-water solution in MAT reactor. (Key:Filled Diamonds-FCC1, Filled Squares-ZSM5, Triangles-ECat,Circles-Al₂O₃, Open Squares-silicon-carbide, Open Diamonds-Y-zeolite.Glycerol feed into reactor as a 50 wt % glycerol-water mixture. Yieldsare based on carbon molar selectivity. Conversion includes coke plusgases plus aromatics.)

FIG. 6 shows the effect of catalyst composition on gas phase yields forthe catalytic cracking of a 50 wt % glycerol-water solution in MATreactor. (Key: Filled Diamonds-FCC1, Filled Squares-ZSM5,Triangles-ECat, Circles-Al₂O₃, Open Squares-silicon-carbide, OpenDiamonds-Y-zeolite. Glycerol fed into reactor as a 50 wt %glycerol-water mixture. Yields are based on carbon molar selectivity.Conversion includes coke plus gases plus aromatics.)

FIG. 7 shows the effect of catalyst composition on theolefin-to-paraffin ratio and C₄ isomer-to-paraffin ratio for thecatalytic cracking of a 50 wt % glycerol-water solution in MAT reactor.(Key: Filled Diamonds-FCC1, Filled Squares-ZSM5, Triangles-ECat,Circles-Al₂O₃, Open Squares-silicon-carbide, Open Diamonds-Y-zeolite.Glycerol fed into reactor as a 50 wt % glycerol-water mixture. Yieldsare based on carbon molar selectivity. Conversion includes coke plusgases plus aromatics.)

FIG. 8 shows the effect of temperature on the catalytic cracking of a 50wt % glycerol-water solution with ZSM-5 catalyst in MAT reactor. (Key:Squares-500° C., Triangles-600° C., Circles-700° C. Glycerol feed intoreactor as a 50 wt % glycerol-water mixture. Yields are based on carbonmolar selectivity. Conversion for pure glycerol feed includes coke plusgases plus aromatics.)

FIG. 9 shows the effect of temperature on gas-phase yields for thecatalytic cracking of a 50 wt % glycerol-water solution with ZSM-5catalyst in MAT reactor. (Key: Squares-500° C., Triangles-600° C.,Circles-700° C. Glycerol fed into reactor as a 50 wt % glycerol-watermixture. Yields are based on carbon molar selectivity. Conversion forpure glycerol feed includes coke plus gases plus aromatics.)

FIG. 10 shows the effect of temperature on olefin-to-paraffin ratio forthe catalytic cracking of a 50 wt % glycerol-water solution with ZSM-5catalyst in MAT reactor. (Key: Squares-500° C., Triangles-600° C.,Circles-700° C. Glycerol fed into reactor as a 50 wt % glycerol-watermixture. Yields are based on carbon molar selectivity. Conversion forpure glycerol feed includes coke plus gases plus aromatics.)

FIG. 11 shows the catalytic cracking of 50 wt % glycerol and 50 wt %sorbitol aqueous solutions using ZSM-5 and silicon-carbide catalysts inMAT reactor at 500° C. (Key: Filled Squares-Glycerol with ZSM-5, FilledTriangles-Sorbitol with ZSM-5, Open Squares-Glycerol with SiC, OpenTriangles-Sorbitol with SiC. Conversion includes coke plus gases plusaromatics.)

FIG. 12 shows the gas phase-yields of 50 wt % glycerol and 50 wt %sorbitol aqueous solutions for catalytic cracking using ZSM-5 catalystin MAT reactor at 500° C. (Key: Squares-Glycerol, Triangles-Sorbitol.Conversion includes coke plus gases plus aromatics.)

FIG. 13 shows the Olefin-to-Paraffin Ratio for 50 wt % glycerol and 50wt % sorbitol aqueous solutions for catalytic cracking using a ZSM-5catalyst in MAT reactor at 500° C. (Key: Squares-Glycerol,Triangles-Sorbitol. Conversion includes coke plus gases plus aromatics.)

FIG. 14 shows the catalytic cracking of mixtures of vacuum gas oil (VGO)with 50 wt % glycerol, using FCC1 catalyst in MAT reactor at 500° C.(Key: Open Squares: Glycerol, Filled Squares: Glycerol-VGO 1-2 VolumeMixtures, Filled Circle: Glycerol-VGO 1-9 Volume Mixtures, and FilledTriangle: VGO. Dotted line represents yields if an additive effect ofglycerol and VGO were observed. Glycerol fed into reactor as a 50 wt %glycerol-water mixture. Yields are based on carbon molar selectivity andmolecular weight of VGO is estimated to be that of phenylheptane.Conversion for VGO and glycerol-VGO mixtures includes gases plus cokeplus gasoline fraction from simulated distillation. Conversion for pureglycerol feed includes coke plus gases plus aromatics.)

FIG. 15 shows the gas phase yields and micromoles H₂ produced incatalytic cracking of mixtures of vacuum gas oil (VGO) with 50 wt %glycerol using FCC1 catalyst in MAT reactor at 500° C. (Key: OpenSquares: Glycerol, Filled Squares: Glycerol-VGO 1-2 Volume Mixtures,Filled Circle: Glycerol-VGO 1-9 Volume Mixtures, and Filled Triangle:VGO. Glycerol fed into reactor as a 50 wt % glycerol-water mixture.Dotted line represents yields if an additive effect of glycerol and VGOwere observed. Yields are based on carbon molar selectivity andmolecular weight of VGO is estimated to be that of phenylheptane.Conversion for VGO and glycerol-VGO mixtures includes gases plus cokeplus gasoline fraction from simulated distillation. Conversion for pureglycerol feed includes coke plus gases plus aromatics.)

FIG. 16 shows olefin-to-paraffin ratios for catalytic cracking ofmixtures of vacuum gas oil (VGO) with 50 wt % glycerol using FCC1catalyst in MAT reactor at 500° C. (Key: Open Squares: Glycerol, FilledSquares: Glycerol-VGO 1-2 Volume Mixtures, Filled Circle: Glycerol-VGO1-9 Volume Mixtures, and Filled Triangle: VGO. Glycerol fed into reactoras a 50 wt % glycerol-water mixture. Yields are based on carbon molarselectivity and molecular weight of VGO is estimated to be that ofphenylheptane. Conversion for VGO and glycerol-VGO mixtures includesgases plus coke plus gasoline fraction from simulated distillation.Conversion for pure glycerol feed includes coke plus gases plusaromatics.)

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

This invention generally relates to a process for fluid catalyticcracking of oxygenated hydrocarbon compounds, comprising the step ofcontacting a reaction feed comprising an oxygenated hydrocarbon compoundwith a fluid cracking catalyst material for a period of less than 3seconds, at a temperature in the range of 300 to 700° C. In a preferredembodiment the contact time is less than 1 second.

The contact time is defined as 1/GHSV, wherein GHSV stands for GasHourly Space Velocity. It will be understood that the contact timereferred herein is the mean contact time of the oxygenated hydrocarboncompounds with the fluid cracking catalyst material. Individualoxygenated hydrocarbon molecules may have contact times that are longeror shorter than the mean. The skilled person will further appreciatethat the mean residence time of the catalyst particles in the reactormay be different from the mean contact time as defined herein; in thesense that the mean residence time of the catalyst particles in thereactor may be longer than the mean contact time, but not shorter.

This invention more specifically relates to a process for production ofolefins, aromatics, syn-gas (hydrogen, carbon monoxide), process heat,alkanes, and coke by co-feeding of glycerol, carbohydrates, sugaralcohols or other biomass derived oxygenated compounds such as starches,cellulose-derived compounds, and hemicellulose-derived compounds withpetroleum derived feedstocks in a standard or modified fluid catalyticcracking process. Mixtures of oxygenated compounds, such as those foundin bio-oils derived from pyrolysis or liquefaction, are also included inthe definition of biomass-derived oxygenated compound. In general,oxygenated hydrocarbon compounds that have been produced via theliquefaction of a solid biomass material are particularly preferred. Ina specific embodiment the oxygenated hydrocarbon compounds are producedvia a mild hydrothermal conversion process, such as described inco-pending application EP 061135646, filed on May 5, 2006, thedisclosures of which are incorporated herein by reference. In analternate specific embodiment the oxygenated hydrocarbon compounds areproduced via a mild pyrolysis process, such as described in co-pendingapplication EP 061135679, filed on May 5, 2006, the disclosures of whichare incorporated herein by reference.

The oxygenated hydrocarbon compounds may be mixed with an inorganicmaterial, for example as a result of the process by which they wereobtained. In particular, solid biomass may have been treated with aparticulate inorganic material in a process such as described inco-pending application EP 061135810, filed May 5, 2006, the disclosuresof which are incorporated herein by reference. These materials maysubsequently be liquefied in the process of EP 061135646 or that of EP061135679, cited herein above. The resulting liquid products contain theinorganic particles. It is not necessary to remove the inorganicparticles from the oxygenated hydrocarbon compounds prior to the use ofthese compounds in the process of the present invention. To thecontrary, it may be advantageous to leave the inorganic particles in theoxygenated hydrocarbon feed, in particular if the inorganic material isa catalytically active material.

It has been found that the reaction feed may comprise significantamounts of water. This is particularly advantageous, because feedstockssuch as bio-oil and glycerol derived from biomass conversion processestend to be mixed with water. For example, a biodieseltransesterification process produces glycerol and water in a 1:3 molarratio. The process of the present invention does not require water to beremoved from the oxygenated material prior to their being fed into thecatalytic cracking reactor.

In a preferred embodiment the reaction feed further comprises a crudeoil-derived material, for example vacuum gas-oil.

The biomass-derived oxygenated compounds can be fed in differentlocations in the FCC process, as shown in FIG. 2, including: (1) in aseparate riser reactor, (2) before introduction of vacuum gas-oil, (3)with vacuum gas-oil, or (4) after vacuum gas-oil on a partiallydeactivated catalyst. In general, best results are obtained when theoxygenated compounds are fed into a separate riser reactor (option (1)),or in the main riser reactor after the vacuum gas-oil (option (4)),because it allows for short contact times of the oxygenated compoundswith the fluid catalytic cracking catalyst material. It is also possibleto feed the oxygenated compound into the stripper.

Injection of glycerol in a parallel-separate reactor to vacuum gas-oil(VGO) cracking allows for an intermediate operation. Before VGOinjection point, very severe cracking conditions (high temperature, highcatalyst to oil ratio) can be encountered. Injecting the biomassfeedstock with VGO can also be done at high or moderate temperatures.After the VGO injection point, or in the stripper, very soft crackingconditions are available (moderate temperature, coked catalyst withreduced activity). The choice of where to inject the VGO feedstock willdepend on the desired products and catalyst used. As discussed inExample 3, feeding the biomass-derived feedstock with the VGO can haveimportant synergistic effects including ethylene, propylene and butaneyields much higher than either VGO or glycerol cracking.

The cracking catalyst material for use in the present invention may be aconventional FCC catalyst material. FCC catalysts generally comprise azeolite, such as zeolite USY, a matrix material, such as alumina, and akaolin clay. The catalyst may further comprise additives for trappingmetal contaminants, for converting sulphur compounds, and the like, aswill be readily understood by a person skilled in the FCC art.

In the alternative the cracking catalyst material comprises a basicmaterial. Examples of suitable basic materials include layeredmaterials, and materials obtained by heat-treating layered materials.Preferably the layered materials are selected from the group consistingof smectites, anionic clays, layered hydroxy salts, and mixturesthereof. Hydrotalcite-like materials, in particular Mg—Al and Ca—Alanionic clays, are particularly preferred. It has surprisingly beenfound that basic materials are suitable for the cracking of a crude-oilderived material, such as VGO, as may be used as a first feedstock incertain embodiments of the process of the present invention.

The basic catalytic materials may be used as such, or may be used inadmixture with a conventional FCC cracking catalyst.

The conversion of biomass-derived oxygenated hydrocarbon compounds inthe FCC process occurs mainly through a series of dehydration, hydrogenproducing, hydrogen consuming, and aromatic forming reactions. In FIGS.3 and 4 we use glycerol to represent biomass-derived oxygenatedhydrocarbon compounds. In this process H₂ may be produced throughsteam-reforming or direct dehydrogenation of the carbohydrates andhydrocarbons, water-gas shift, and decarbonylation of partiallydehydrated species as shown in FIG. 3. These reactions may produce CO,CO₂, and coke as well as hydrogen. The hydrogen produced in thesereactions may be consumed in reactions that increase the H/C_(eff) ratioof the products as shown in FIG. 4, leading to olefins and alkanes.Hydrogen may be exchanged directly through hydrogen transfer reactionsbetween two hydrocarbon/carbohydrates chains, or through consecutivedehydrogenation/hydrogenation processes. Hydrogen transfer reactionsoccur on acid sites, while dehydrogenation/hydrogenation reactions aregreatly accelerated by the presence of a metal. Aromatics are producedduring this process probably by a diels-alder reaction and condensationof olefins and partially dehydrated/hydrogenated species. To selectivelyproduce olefins and aromatics, the dehydration, hydrogen producing andhydrogen transfer reactions must be properly balanced by choosing theproper catalysts and reaction conditions.

The process of the present invention provides (1) fuels that areobtained from sustainable biomass resources, (2) a reduction in CO₂emissions from petroleum plants, (3) a reduction of the amount ofpetroleum feedstocks in a petroleum refinery and (4) utilization of FCCtechnology that is already developed and in use in petroleum refineriestherefore co-feeding of biomass into an FCC unit would not require asignificant capital investment.

EXAMPLES

The following Examples are included solely to provide a more completedisclosure of the subject invention. Thus, the following Examples serveto illuminate the nature of the invention, but do not limit the scope ofthe invention disclosed and claimed herein in any fashion.

Experiments described herein were performed in a Microactivity test(herein referred to as MAT). [Corma, 1990 #15]. The reaction zone andproduct recovery system were designed in accordance with ASTM D-3907.Before each experiment the MAT system was purged with a 50 ml/min N₂flow during 30 min at the reaction temperature. After reaction,stripping of the catalyst was carried out for 15 min using a N₂ flow of40 ml/min. During the reaction and stripping steps, the liquid productswere collected in the corresponding glass receivers located at the exitof the reactor, kept at a temperature of 278 K by means of acomputer-controlled bath. Meanwhile the gaseous products were collectedin a gas burette by water displacement. After stripping, the catalystwas regenerated at a temperature of 813 K for 3 hours, in a 100 ml/minstream of air. The gases were analyzed using a Varian 3800-GC equippedwith three detectors, a Thermal Conductivity Detector (TCD) for analysisof H₂ and N₂, which were separated in a 15 m molecular sieve column, anda Flame Ionization Detector (FID), and for C₁ to C₆ hydrocarbonsseparated in a 30 m Plot/Al₂O₃ column. Simulated distillation of theliquids was carried out with a Varian 3800-GC following the ASTM-2887-Dprocedure. Cuts were made at 423.8 K for light gasoline, 489.3 K forheavy gasoline and 617.1 K for LCO. The CO₂ formed during theregeneration step was monitored and quantified by means of an IR cell.

Carbon yields are defined below as the moles of carbon in the produceddivided by the moles of carbon in the feed. All conversions below arereported on a per carbon basis. Hydrogen selectivity defined below asthe moles of hydrogen divided by the potential moles of hydrogenproduced. The potential moles of hydrogen produced are the moles ofproduced carbon times the hydrogen to carbon ratio in the feed plus themoles of CO₂ produced.

Six different catalysts were used for these examples. Thephysical-chemical characteristics of the six solids used in this studyare presented in Table 1. They include a fresh commercial FCC catalystscontaining Y-zeolite in a silica-alumina matrix (FCC1), a commercialequilibrium FCC catalysts with V and Ni impurities (ECat), Al₂O₃, a Yzeolite (Y), a ZSM-5 FCC additive (ZSM5), and a low-surface area inertsilicon carbide (SIC). Ecat had a metal content of 4400 ppm V and 1600ppm Ni. The FCC1 catalyst was laboratory-deactivated during 4 hours at816° C. under a steam-vapor atmosphere, and had no contamination metalcontent. The Y-zeolite was CBU 500, steamed for 4 h at 816° C. The ZSM-5zeolite was mixed with a clay binder, to around 15% weight. A glycerolsolution was prepared with 99.5 weight percent glycerol (AldrichChemicals) diluted at a 1:1 weight ratio (about a 1:5 molar ratioglycerol/water) with distilled water. A sorbitol solution was preparedwith 99% sorbitol and the same water 1:1 weight ratio water dilution.

TABLE 1 Catalytic properties of catalysts used Micropore BET SurfaceParticle Volume Catalyst Si/Al Area (m²/g) Size (cm³/g) FCC1 13 290 0.10.087 ECat 20 156 0.1 0.050 ZSM-5 additive 50 70 0.1 0.027 Al₂O₃ 0 1500.2-0.4 0 Y-Zeolite 12 400 0.2-0.4 0.122 Silicon Carbide — <1 0.4-0.8<0.001 (SiC)

Example 1

Six different catalysts were tested for catalytic cracking of an aqueous50 wt % glycerol as shown in FIGS. 5-7, including FCC1, ECat, Al₂O₃, Y,ZSM75, and SiC. The products for the FCC1 catalyst include coke, gases,and liquid products. Between 30-50% of the carbon in the glycerol feedwas converted into coke for the FCC1 catalyst (FIG. 5). The coke yieldincreased as the conversion increased, while the aromatic yielddecreased as the conversion increased for the FCC1 catalyst. This may bedue to formation of coke from the aromatic compounds. The gas phaseyields for FCC1 decreased fromCO>propylene>CO₂>ethylene>butene>methane>ethane>propane>n-butane (FIG.6). Alkanes and olefins were produced together with aromatics and coke,which indicates that hydrogen transfer reactions have a strong impact onthe final product distribution. The C₃ and C₄ olefin-to-paraffin ratiofor FCC1 was greater than 10 as shown in FIG. 7.

Petroleum-derived feeds typically contain metal impurities (V, Ni andFe), which deposit themselves onto the catalyst during the FCC reaction.Thus, in order to study the potential effect of metals (mainly V and Ni)on product distribution, we tested a FCC equilibrium catalyst(ECAT)containing 4400 ppm V and 1600 ppm Ni. This catalyst gave a loweractivity than the fresh FCC1 catalyst, as could be expected from thehigher content of zeolite and surface area of the latter. However, theproduct selectivity for the FCC1 and ECAT catalyst was very similar,indicating that V and Ni have little or no catalytic effect. Thermalcracking of glycerol was studied by using an “inert” SiC material. Thelow activity of the “inert” SiC shows that glycerol has a high thermalstability, and thermal reactions are negligible in comparison to thecatalytic transformation.

FCC catalysts contain Al₂O₃, SiO₂—Al₂O₃ and Y-zeolite in the catalystmatrix. The Al₂O₃ catalyst had similar gas and coke yields as the FCC1and ECat catalysts. The gas-phase yields for Al₂O₃ where also similar tothose of FCC1 and ECat, with the exception that Al₂O₃ has higher H₂ andethane yields, and lower propylene, n-butane, butane, and aromaticyields, than FCC1 and ECat.

The Y-zeolite had a catalytic activity similar to the FCC1 catalyst. Thefact that high conversions were obtained with the Y-zeolite and γ-Al₂O₃catalysts shows that dehydration reactions can occur readily on bothBronstedt and Lewis acid sites. When comparing the pure zeolitecomponent with the FCC1 catalyst it can be seen that the coke yield wasslightly higher for Y-zeolite than FCC1. The aromatic yield was lowerfor the Y-zeolite than for FCC1. The other differences between Y-zeoliteand FCC1 are that the Y-zeolite gave a lower CO₂ yield and higher C₁-C₄alkane and H₂ yields than the FCC1 catalyst. The olefin yields for theY-zeolite and FCC1 catalyst were similar, therefore the olefin toparaffin ratios for the Y-zeolite were lower than the FCC1 catalyst.

ZSM-5 is a well known catalyst additive for FCC catalysts, so we alsotested the activity of the ZSM-5 catalyst for catalytic cracking ofglycerol. The major difference with ZSM-5 and the other catalysts testedis that ZSM-5 had a lower coke yield (less than 20%) and gave a higheryield of gases and aromatics. This is probably due to the smaller poresize of ZSM-5 zeolite, which makes it difficult for larger aromatic cokeprecursors to form inside the small ZSM-5 pores. The activity of thecatalysts (in terms of total conversion to gases, coke, and aromatics)decreased as Y˜FCC1>Al₂O₃>ZSM5>ECat>>SiC. The gas yields decreased inthe order ZSM-5>>ECat>FCC1>Al₂O₃˜Y. The aromatics yield increasedlinearly with conversion for the ZSM5 catalyst, but first increased andthen decreased with further increasing conversion for the FCC1, Y, ECatand Al₂O₃ catalysts. It has been extensively shown with hydrocarboncracking that the small ZSM-5 zeolite pore channels make it difficultfor aromatics to condensate. Higher yields of coke were seen on the Y,ECat and FCC1 catalysts, due to the larger cage diameter of theY-zeolite catalyst as well as an extensive mesopore volume which allowshigher aromatics condensation, leading to coke formation. The gasphase-carbon yields for ZSM5 decreased in the orderCO>ethylene>propylene>CO₂>butene>methane>ethane>propane>n-butane. TheZSM5 catalyst gave a much higher ethylene yield and lower methane yieldthan the other catalysts, which may indicate that, on ZSM5, ethylene maybe formed through decarbonylation of an oxygenated intermediate ratherthan via the cracking of longer chain hydrocarbons.

The olefin-to-paraffin ratio for these catalysts was greater than 10 inmost cases, as shown in FIG. 7. The olefin-to-paraffin ratio for C₂compounds was extremely high (e.g. greater than 60) for the ZSM5catalyst. For the ECat and FCC1 catalyst the C₃ and C₄ olefin toparaffin ratio decreased as the conversion increased, which goes inparallel with the increases in coke. The olefin-to-paraffin ratio foriso-C₄ compounds decreased in the order Al₂O₃>FCC1>ECat>ZSM5>Y.

Example 2

FIGS. 8-10 show the effect of temperature on the catalytic cracking ofglycerol with ZSM5. The activity for cracking of glycerol increased withtemperature, as shown in FIG. 8. As the temperature increased, the cokeyield significantly decreased (FIG. 8), and the CO, H₂, and ethyleneyields increased (FIG. 9). Similar temperature effects were observed forcatalytic cracking of glycerol with FCC1. At 500° C. the coke yieldincreased linearly with conversion, whereas at 600 and 700° C. the cokeyield did not increase with conversion. The aromatics at 500° C. alsoincreased linearly with conversion, whereas at 600 and 700° C. theydecreased linearly with conversion, probably as the result of a lowercontribution of olefin oligomerization and hydrogen transfer (bothexothermic reactions) when the reaction temperature was increased. Thegas yield increased with both conversion and temperature.

Example 3

To test the catalytic cracking of other biomass-derived oxygenatedhydrocarbon compounds we used sorbitol as a feed, with ZSM5 and SiC ascatalysts. Sorbitol has a lower H/C_(eff) ratio than glycerol. FIGS.11-12 show the results of aqueous solutions of 50 wt % sorbitol and 50wt % glycerol feeds in the MAT reactor. The thermal stability ofglycerol is greater than that of sorbitol. However, surprisingly,sorbitol and glycerol had similar coke, gas and aromatic yields eventhough they have different H/C_(eff) ratios.

The gas phase yields for glycerol and sorbitol are shown in FIG. 12. Themain differences between the two feeds are that sorbitol had a higher COyield than glycerol feeds with the ZSM-5 catalyst. The CO and CO₂ yieldis also higher for the thermal sorbitol reaction with SiC as the“catalyst” (1-2% CO yield at conversions 4-18) than for glycerol(0.3-0.5% CO yield at conversions 2-8%). More hydrogen is required toconvert sorbitol into a paraffin or olefin than is the case forglycerol, therefore hydrogen producing reactions (such as CO production)should be greater for sorbitol than for glycerol at similar olefin andparaffin yields. Sorbitol also had a lower ethylene yield than glycerol,with the yields of the other hydrocarbons being fairly similar.

Example 4

To simulate co-feeding of biomass-derived oxygenated hydrocarboncompounds with VGO, we processed pure VGO and mixtures of VGO withglycerol as feedstocks in the MAT reactor with the FCC1 catalyst at 500°C., as shown in FIGS. 13-15. In all the mixtures, a 50 wt % glycerol inwater solution was used. The mixed feeds consisted of 9:1 and 2:1VGO/glycerol-solution mixtures (volumetric ratios), which corresponds tomolar carbon ratios of VGO/glycerol of 31:1 and 7:1, respectively. Theconversion in these figures includes the gases, coke and gasolinefraction for VGO and VGO mixtures. For the pure glycerol feed theconversion includes gases, coke and aromatics. The catalyst-to-feedratio in FIG. 17 includes in the feed weight the weights of both theglycerol solution and the VGO.

As shown in FIG. 17, the glycerol solution gave a higher yield to gas,aromatics and coke than VGO. An increase in the amount of glycerol inthe VGO-glycerol mixtures slightly increased the conversion. Selectivityeffects were barely seen with the 9:1 VGO-glycerol mixture. Apparentlythe amount of biomass was too small to produce significant changes inthe different yields. However, the 2:1 VGO-glycerol mixture introducedan important dilution of the VGO feedstock (at least 3/1 molar ratiobetween VGO feed molecules and glycerol/water mixture), and significanteffects on gas and coke yields were observed. Included as a dashed linein FIGS. 18-19 are the theoretical product yields obtained if glyceroladdition to VGO were purely additive (which we will call additiveeffect). This effect was calculated adding the yields obtained with theglycerol solution and VGO runs, with respect to the mass ratio of bothfeeds, and normalizing to 100%.

One of the major differences between VGO and glycerol is that glycerolproduces more coke, ethylene and propylene than VGO. Adding glycerol toVGO significantly increased the amount of coke, but in a proportionsimilar to what would be observed as an additive effect. Addition ofglycerol to VGO did not change the gasoline yield, but did decrease thelight cycle oil (LCO) yield because of a dilution effect with theglycerol feed, as glycerol cracking does not produce LCO fragment butsome gasoline-range fragments, including some oxygenated hydrocarboncompounds.

A surprising effect from this example is that the ethylene and propyleneyields for the VGO/glycerol mixtures was higher than what would beexpected from an additive effect, as shown in FIG. 14. Compared to theVGO, glycerol cracking produced significant amounts of CO and CO₂, asimilar yield of hydrogen, more methane and ethylene but less ethane,more propylene but less propane, and much less butanes and butane.

Example 5

To simulate feeding of biomass-derived oxygenated hydrocarbon compoundsafter VGO injection, we cracked a 50 wt % glycerol solution in a MATreactor on a FCC1 which had coke deposited onto it before the test, asshown in Table 2. The coke was deposited onto the catalyst in a MATreactor with heavy gas oil, without the customary regeneration step,prior to passing the glycerol solution. The coke content of the catalystbefore the test was 2.0 weight percent. The pre-coked catalysts had alower coke yield than the fresh catalyst, as shown in Table 2. However,the pre-coked catalyst exhibited a lower activity than the freshcatalyst. The gas yield obtained with the coked catalyst at a Cat/Feedratio of 4 was similar to the gas yield of a fresh catalyst obtained ata catalyst-to-feed ratio of 1.5. Yields of the different gas fractionswere similar for the hydrocarbons, while more CO and less CO₂ wereproduced on the coked catalyst. Aromatic selectivity were also quitesimilar for both the fresh and coked catalysts.

TABLE 2 Conversion of 50 wt % aqueous glycerol Solution in MAT reactorat 500° C. for 30 seconds with FCC1 catalyst. Catalyst Coked Coked FreshFresh Fresh Fresh Cat/Feed 4.0 8.0 1.5 2.0 3.0 4.0 % Conv. Gas 19.9 25.421.5 24.1 34.4 36.2 % Conv. Coke 19.0 10.6 36.6 39.7 50.2 52.0 % Conv.9.1 3.7 9.8 7.3 4.9 5.1 Aromatics Carbon Yields (%) CO 7.54 8.54 8.098.25 10.15 10.16 CO₂ 2.40 1.16 3.11 3.77 5.54 5.96 Methane 1.30 1.911.31 1.38 2.22 2.36 Ethane 0.49 0.64 0.48 0.50 0.74 0.75 Ethylene 1.873.25 2.10 2.44 3.96 4.45 Propane 0.11 0.17 0.12 0.14 0.24 0.28 Propylene4.19 6.58 4.44 5.36 8.10 8.60 N-Butane 0.02 0.03 0.01 0.02 0.05 0.06Iso-Butane 0.04 0.04 0.03 0.04 0.12 0.18 Butenes 1.91 3.00 1.8 2.2 3.33.4 H₂ Yield 1.2 2.9 1.4 1.9 3.0 3.0

Example 6

A simulation at very high temperature (740° C.) and very low spacevelocity (compared to typical conditions in FCC) was carried out, tosimulate the injection of a small quantity of a glycerol/water mixture.The very severe conditions were aimed at maximizing the olefin yieldfrom glycerol, as well as lowering the amount of gasoline rangeoxygenates produced by glycerol processing so that it interacts with VGOprocessing as few as possible. Results are summarized in table 3.

TABLE 3 Operating condtions Temperature (° C.) 720 WHSV (h⁻¹) 15 yields,wt % Carbon monoxide 50.6 Carbon dioxide 8.8 Methane 10.9 Ethane 1.4Ethylene 13.1 Propane 0.1 Propylene 4.9 Butenes 0.4 Oxygenates 0.7 C5+hydrocarbons 1.1 coke 7.9

REFERENCES CITED

-   Adjaye, J. D., S. P. R. Katikaneni, et al. (1996). “Catalytic    conversion of a biofuel to hydrocarbons: effect of mixtures of    HZSM-5 and silica-alumina catalysts on product distribution.” Fuel    Processing Technology 48: 115-143.-   Gayubo, A. G., A. T. Aguayo, et al. (2004). “Transformation of    Oxygenate Components of Biomass Pyrolysis on a HZSM-5 Zeolite I.    Alcohols and Phenols.” Ind. Eng. Chem. Res, 43: 2610-2618.-   Gayubo, A. G., A. T. Aguayo, et al. (2004). “Transformation of    Oxygenate Components of Biomass Pyrolysis Oil on a HZSM-5    Zeolite. II. Aldehydes, Ketones, and Acids.” Ind. Eno. Chem. Res.    43: 2619-2626.-   Gayubo, A. G., A. T. Aguayo, et al. (2005). “Undesired components in    the transformation of biomass pyrolysis oil into hydrocarbons on an    HZSM-5 zeolite catalyst.” Journal of Chemical Technology and    Biotechnology 80: 1244-1251.-   Katikaneni, S. P. R., J. D. Adjaye, et al. (1995). “Performance of    Aluminophosphate Molecular Sieve Catalysts for the Production of    Hydrocarbons from Wood-Derived and Vegetable Oils.” Energy and Fuels    9: 1065-1078.-   Sharma, R. K. and N. N. Bakhshi (1993). “Catalytic Upgrading of    Pyrolysis Oil.” Energy and Fuels 7: 306-314.-   Srinivas, S. T., A. K. Dalai, et al. (2000). “Thermal and Catalytic    Upgrading of a Biomass-Derived Oil in a Dual Reaction System.”    Canadian Journal of Chemical Engineering 78: 343-354.

What is claimed is:
 1. A process for converting biomass to reactionproducts, the process comprising: (a) contacting biomass-derivedoxygenated hydrocarbon compounds with an inorganic material havingcatalytic properties, wherein the inorganic material includes kaolin andat least one zeolite, wherein the biomass-derived oxygenated hydrocarboncompounds comprise cellulose-derived compounds and/orhemicellulose-derived compounds; and (b) converting the biomass-derivedoxygenated hydrocarbon compounds to reaction products in the presence ofthe inorganic material, wherein the contact time between thebiomass-derived oxygenated hydrocarbon compounds and the inorganicmaterial in step (b) is less than 3 seconds.
 2. The process of claim 1,wherein the at least one zeolite includes zeolite-USY, beta-zeolite,ZSM-5, zeolite Y, or a combination thereof.
 3. The process of claim 1,wherein the at least one zeolite includes ZSM-5.
 4. The process of claim1, wherein the biomass-derived oxygenated hydrocarbon compounds includecompounds produced from solid biomass via at least one process chosenfrom pyrolysis, liquefaction, and a hydrothermal conversion process. 5.The process of claim 1, wherein the biomass-derived hydrocarboncompounds are produced from solid biomass via a pyrolysis reaction. 6.The process of claim 5, wherein the biomass-derived hydrocarboncompounds are produced from solid biomass via a pyrolysis reaction,wherein the biomass-derived hydrocarbon compounds comprisehemicelluloses-derived compounds.
 7. The process of claim 6, wherein thesolid biomass is wood.
 8. The process of claim 1, wherein step (b) iscarried out at a reaction temperature ranging from 300° C. to 700° C. 9.The process of claim 1, wherein the reaction products include liquidreaction products, gaseous reaction products, or a combination of liquidand gaseous reaction products.
 10. The process of claim 1, wherein thereaction products include at least one of olefins, aromatics, alkanes,coke, hydrogen gas, or carbon monoxide gas.
 11. The process of claim 1,wherein the contact time between the biomass-derived oxygenatedhydrocarbon compounds and the inorganic material in step (b) is lessthan 1 second.
 12. The process of claim 1, further including directingthe biomass-derived oxygenated hydrocarbon compounds into a riserreactor, wherein step (b) includes converting the biomass-derivedoxygenated hydrocarbon compounds in the presence of the inorganicmaterial to the reaction products in the riser reactor.
 13. The processof claim 1, wherein the reaction products include a fuel.
 14. A processfor converting biomass to reaction products, the process comprising: (a)contacting biomass-derived oxygenated hydrocarbon compounds with aninorganic material having catalytic properties, wherein the inorganicmaterial includes kaolin and at least one zeolite, wherein thebiomass-derived oxygenated hydrocarbon compounds comprisecellulose-derived compounds and/or hemicellulose-derived compounds; (b)converting the biomass-derived oxygenated hydrocarbon compounds toreaction products in the presence of the inorganic material in a reactorsystem; and (c) combining the biomass-derived oxygenated hydrocarboncompounds and the inorganic material with a crude oil-derived materialin the reactor system, wherein step (b) includes converting thebiomass-derived oxygenated hydrocarbon compounds to the reactionproducts in the presence of the inorganic material and the crudeoil-derived material.
 15. The process of claim 14, wherein the crudeoil-derived material is vacuum gas oil.
 16. A process for convertingbiomass to reaction products, the process comprising: (a) introducingsolid biomass comprising hemicellulose into a pyrolysis reactor; (b)converting the solid biomass to biomass-derived compounds via pyrolysisin the pyrolysis reactor, wherein the biomass-derived compounds comprisehemicellulose-derived compounds; and (c) converting the biomass-derivedcompounds in the presence of an inorganic material having catalyticproperties to reaction products, wherein the inorganic material includeskaolin and at least one zeolite.
 17. The process of claim 16, whereinthe at least one zeolite includes zeolite-USY, beta-zeolite, ZSM-5,zeolite Y, or a combination thereof.
 18. The process of claim 6, whereinthe at least one zeolite includes ZSM-5.
 19. The process of claim 16,wherein step (c) is carried out at a reaction temperature ranging from300° C. to 700° C.
 20. The process of claim 16, wherein the reactionproducts include liquid reaction products, gaseous reaction products, ora combination of liquid and gaseous reaction products.
 21. The processof claim 16, wherein said pyrolysis reactor comprises a riser reactorand the converting of steps (b) and (c) are both carried out in theriser reactor.
 22. The process of claim 16, further including contactingthe biomass and the inorganic material with a crude oil-derived materialin the pyrolysis reactor, wherein steps (b) and (c) are carried out inthe presence of the inorganic material and the crude oil-derivedmaterial.
 23. The process of claim 22, wherein the crude oil-derivedmaterial is vacuum gas oil.
 24. The process of claim 16 wherein thehydrocarbons contained in the reaction products have a higher effectivehydrogen to carbon ratio (H/C elf) than the biomass or biomass-derivedcompounds.
 25. The process of claim 16, wherein the biomass-derivedcompounds comprise cellulose-derived compounds.
 26. The process of claim16, wherein step (b) is carried out in the presence of the inorganicmaterial.
 27. The process of claim 16, wherein the solid biomass iswood.